Benzoic acid, 4-fluoro-, ethyl ester → HCID 18376029, compound

HRID 2300186Notes

Reaction equation

HRID 2300186 reaction equation
[C:1]([C:3]1[CH:4]=[N:5][C:6]([CH3:9])=[CH:7][CH:8]=1)#[N:2].[F:10][C:11]1[CH:21]=[CH:20][C:14]([C:15](OCC)=[O:16])=[CH:13][CH:12]=1.C(=O)=O.C(O)C.C[Si]([N-][Si](C)(C)C)(C)C.[Li+]>C1COCC1.O>[F:10][C:11]1[CH:21]=[CH:20][C:14]([C:15](=[O:16])[CH2:9][C:6]2[CH:7]=[CH:8][C:3]([C:1]#[N:2])=[CH:4][N:5]=2)=[CH:13][CH:12]=1

Participants

7

Reactant 4

HCID 67976Benzoic acid, 4-fluoro-, ethyl esterHCID 2819956-Methylpyridine-3-carbonitrileHCID 2733832Lithium HexamethyldisilazideHCID 19604758Methanedione--ethanol (1/1)

Product 1

HCID 18376029HCID 18376029, compoundYield 205.4%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent

Procedure

To a solution of 3-cyano-6-methylpyridine (High Force Research Limited) (0.59 g 1,5 mmol) and ethyl 4-fluorobenzoate (0.84 g 5 mmol) (Aldrich) in dry THF (15 ml) stirring under nitrogen at −70° (Dricold/ethanol) was added dropwise lithium bis(trimethylsilyl)amide (10 ml M solution in hexane 10 mmol). The reaction was allowed to warm to room temperature, stirred under nitrogen for 20 hr, poured into water (200 ml) and extracted with ethyl acetate (3×50 ml). The combined extracts were washed with water (50 ml), brine (50 ml) and dried (MgSO4). Removal of solvent gave a solid which was crystallised from ethanol to give the title compound as a yellow solid (0.74 g 62%) which existed as a mixture of keto- and enol-forms by NMR. MH+: 241; mp: 170-1710 (uncorrected)

Workup

  1. extractionextracted with ethyl acetate (3×50 ml)
  2. washThe combined extracts were washed with water (50 ml), brine (50 ml)
  3. dry with materialdried (MgSO4)
  4. customRemoval of solvent
  5. customgave a solid which
  6. customwas crystallised from ethanol

Sources & evidence

ORD record
ord-c2d5bffd52114411bc77f483506dc4ef
Source dataset
uspto-grants-2002_12
Patent number
US06498166B1

Reaction notes

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